Process of making azo dyes containing fatty acid radicals.



UNITED STATES PATENT OFFICE. l I NATHAN SI-ILZBERGER, or NEW YORK, N. Y. i g i r'nocnss or azo nYn's oo 'ranrnre ram? Iranians.

I To all whom. it may concern:

' Specification of Letter'i Patent.

Application filed October 8, 1907. Said No. 895,507.

' Patented Oct. 27',

Be it known that I, NATHAN Surznnaonn, a citizen of theUm'ted States, residing at No.

34 West Seventy-first street, New York city,

New York, United States of America, have invented new and useful Im rovements in Processes for the Production 0 A20 Dyestuffs Containing the Radicals of Higher Fatty Acids,.of which the followingis as ecification.

In the application, Serial l\o. 364,737, filed by me March 26th 1907, a process forthe production of azo dyes containing the or phenols and derivatives of same.

radical of a higher fatty acid is described.

The therein described process consists in the.

combination of diazo compounds containing the radical of a higher fatty acid with amins It has now been found that azo dyes containing the radical of a fatty acid can also be obtained by combining a diazo salt with an amin or a derivative of such an amin (as amido-phenol, a diamin) which amin, etc. contains the radical of a fatty acid, and not only as described in Serial No. 364,737, by combining a diazotized compound which contains the radical of the fatty acid with an amin or phenol or their derivatives-which do not contain such fatty acid radicals. The amins which are to be considered in the present case may contain besides the amid group in which the radical of the fatty acid is located, one ormore other amino or phenol groups or phenol and amid groups at the same time. The azo dyes obtained .in the present application are entirely similar in character to those described in application, Serial No. 364,737.

In a number of cases the present process, however, ofi'ors advantages over and above the old process; as the raw materials here requircd are very often cheaper and more easily to be had and as the formation of certain dyes often quicker and the yields better than in the former process. The fatty acids which aroused in manufacturing these azo colors are those contained in natural vegetable and animal fats and oils, principally stearic, palmitic and oleic acids and their mixtures. The acid radical of one of these acids is introduced into the aromatic amin or derivative of sameamidophenol, p-phenylendiamin, benzidinior naphthylam in-substituting an atom of hydrogen in the amido group. It is, however, not necessary that the amin at the time when the radical of the fatty acid is introduced, contains any other amido or phenol group.

after the fatty acid has been introduced, '5. 'e. by nitratin the amin after it already con- Such additional amido or phenol group or groups of both may be introduced, later on tains the atty acid radical, reducing the I ensuing nitro compound and in case an tion product) of the fatty acid arylid is obtained, which is then connected with the diazo compound. In regard to the diazo com ounds which are to be usedv in the pres ent here described process and to be brought into reaction with the amino or oxy fatty acid 'arylids, any diazo salt canbe used.

' Examples.

(1) 50 gr. stearic acid are heated with a reflux condenser with somewhat more than one molecule of anilin to about 250 for about 4 to 5 hours. After removing the reflux con denser the temperature is raised to about 280 and the su erfluous anilin which has not reacted with t e acid is distilled off. The thus obtained stearic acid anilid is dissolved in 600 to 700 gr. cone. H 80 preferably at a temperature where the anilid is .just in a moltenstate. Care should be taken in mixing the anilid with the acid. Into this solution is slowly added at ordinary tem erature (if necessary cool) a little more t an one molecule of nitric acid. After addin the nitric acid the mixture is slowly poure into cold water which is being continually stirred, whereby the nitrated anilid of thestearic acid separates out as a yellow mass. It is now freed as much as possible from the water, dissolved in alcohol and the nitro grou reduced by means of metals and acid (wit iron and hydrochloric acid). The thus obtained amido stearic acid anilid is brought in reaction with any diazo salt. If diazobenzolchlorid is used a yellow dye of a fatty character is formed.

(2) The same azo dye is obtained when stearic acid is heated together with p-phenylendiamin and the hereby formed p-amino anilid of the stearic acid is brought into reaction with diazobenzolchlorid; 4 gr. stearic acid are melted together with 2 gr. of p-phevoxy group is desired 'in' substituting the nylendiamin (theory 1. 5 gr.) for from 1 5 to minutes at a temperature of about 200. The com ound thus obtained crystallized from alco ol, finely suspended in warm water and brought in reaction with diaaobenzolarylid of a fatt acid which can be connected "-withadiazo s t whereby a rs fatty character. .1

an azo dye ensues 112(4) =Diamins and benzidin can also be 7 used inithunanufacture of these fatty azo -;-pe1'fature of 0. into coldwateriand the yellow crystalline sfi-fcompoundwhichxis precipitated, is filtered ofisand washed free from the acids.

dyesas they, .when connected withv a fattyacid and reacting with a diazo saltyform also azo dyes of a fatty kind.

(5) Naphthylamin can also be employed as followsz-5 gr. palmitic acid are eated together with-somewhat more than one molecule of naphthylamin (theory 2.8 gr.) at a temperature of about 250 water is visibly s 'lit off. The temperature is finally raised to 300 whereby most of the superfluous n'aphthylamin' sublimes away. The resulting compound recrystallized from alcohol is obtained in colorless crystals which is dissolved in about 100 gr. conc. sulfuric acid and nitrated with one molecule of nitric acid taking 3.8 cc. (specific gravity 1.17) at a tem- ".E -:The liquid is now poured After dissolving in alcohol it is reduced with zinc and hydrochloric acid to the colorless amin body which-separates out from the liquid after the zinc mud has been filtered ofi, on the addition of water. This amido body finely suspended in water which has been aciduv lated with acetic acid is added to a solution (6) 5' gr. palmiticacid are melted together with"2.2 gr.bp-aminophenol, at about 200 water is visi y split off. The temperature is gradually raised to about 250 constantly stirring and heated as long as steam bubbles are discharged. On cooling the reddish brown liquid solidifies to agraymass which is recrystallized from alcohol. Finely divided in water the oxyanilid after the addition of an alkali is brought into reaction with diazobenzolchlorid. An azo d' e of reddish brown shade was obtained of a atty character as the other dyes herein described.

The ualities and uses of the hereundescribed atty azo dyes are entirely similar to in the given examples, the shades of the ensuin dyes are generally deeper.

hat I claim and desire to secure by Letters Patent of the United Statesis:

1. A process for the production of azo dye stuffs containing the radicals of fatty acids occurring in fats and oils, consisting in coupling diazo compounds with oxy-and-aminoderivatives of arylids containing the radical of such fatty acids as occur in animal and vegetable fats and oils, substantially as described, and for the purpose set forth.

2. A process for the production of azo dye stuffs containing the radicals of fatty acids occurring in fats and oils, consisting in coupling diazo compounds with oXy-and amino derivatives of arylidscontaining the radicals of mixtures of fatty acids occurring in animal and vegetable fats and oils, substantially as described and for the purpose set forth.

In witness whereof I have hereunto signed my name this 19th day of September 1907,

in the presence of two subscribing witnesses.

NATHAN SULZBERGER.

Witnesses 1 HENRY HAsPER, WOLDEMAR HAUPT 

